Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
  • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/10—Homopolymers or copolymers of propene
  • C08L23/12—Polypropene

Definitions

• the present invention relates to a poly-1-butene resin composition and a pipe comprising the composition. More particularly, the invention relates to a poly-1-butene resin composition having excellent high-speed moldability into a pipe such as a cold or hot water pipe, particularly a cold or hot water supply color pipe, and also relates to a pipe comprising the composition.
• a poly-1-butene resin is favorable for cold or hot water pipes such as cold or hot water supply pipes because it is excellent in creep properties at high temperatures and stress cracking resistance and has flexibility and good workability.
• the cold or hot water supply pipes are usually obligated to be colored according to the standard, e.g., JIS in Japan, and the main color of the pipes is beige.
• the cold or hot water supply pipes mainly have small to medium bore diameters (approx. 8 - 50 mm).
• the molding rates to produce the pipes differ with the sizes of the pipes.
• the cold or hot water supply pipes have heretofore been produced by the use of a resin composition comprising a poly-1-butene resin, a pigment and as a pigment dispersant a low-density ethylene/propylene copolymer wax or a wax obtained by thermal decomposition of high-pressure low-density polyethylene (HPLDPE).
• This resin composition is inferior to a poly-1-butene resin containing no pigment and no pigment dispersant in the high-speed moldability into pipes.
• the use of the poly-1-butene resin containing no pigment makes it possible to produce a pipe having an outer diameter of 15 mm and an inner diameter of 11 mm at a rate of 25 m/min.
• the resin composition comprising poly-1-butene, a pigment (gray color) and as a pigment dispersant an ethylene/propylene copolymer wax or a wax obtained by thermal decomposition of HPLDPE, the limit'of the molding rate to produce a color pipe having an outer diameter of 15 mm and an inner diameter of 11 mm is 18 m/min.
• the resin composition comprising the poly-1-butene resin, the pigment and the ethylene/propylene copolymer wax is inferior to the poly-1-butene resin containing no pigment in the high-speed moldability, and the reason is that the addition of the pigment to the poly-1-butene resin makes a die swell ratio larger in the molding process and the resulting pipe catches in the sizing zone of the extrusion molding machine to meet with large resistance.
• the present inventors have earnestly studied in order to obtain such a poly-1-butene resin composition containing a pigment as is capable of producing a cold or hot water supply pipe at a molding rate almost equal to or higher than that of the poly-1-butene resin containing no pigment, and as a result, they have found that the die swell ratio having an influence on the pipe molding rate depends greatly upon the type of the pigment dispersant contained in the poly-1-butene resin composition.
• the present inventors have further studied and found that:
• a poly-1-butene resin composition which comprises a poly-1-butene resin having a specific melt flow rate and polyethylene having a viscosity-average molecular weight (Mv) of 900 to 29,000 and/or polypropylene having a viscosity-average molecular weight (Mv) of 900 to 29,000 and in which the content of the polyethylene and/or the polypropylene is in the range of 0.001 to 5 parts by weight based on 100 parts by weight of the poly-1-butene resin, a pipe having an outer diameter of 15 mm and an inner diameter of 11 mm can be produced at a higher rate (e.g., 33 m/min) than that of the conventional poly-1-butene resin containing no pigment, and
• a poly-1-butene resin composition which comprises a poly-1-butene resin having a specific melt flow rate, a pigment and homopolyethylene having a viscosity-average molecular weight (Mv) of 900 to 29,000 and/or homopolypropylene having a viscosity-average molecular weight (Mv) of 900 to 29,000 as a pigment dispersant and in which the content of the homopolyethylene and/or the homopolypropylene is in the range of 0.001 to 5 parts by weight based on 100 parts by weight of the poly-1-butene resin, a pipe having an outer diameter of 15 mm and an inner diameter of 11 mm can be produced at a rate of 33 m/min.
• the present invention is intended to solve such problems associated with the prior art as described above, and it is an object of the invention to provide a poly-1-butene resin composition having excellent high-speed moldability into a pipe such as a cold or hot water pipe, particularly a cold or hot water supply color pipe. It is another object of the invention to provide a pipe comprising the composition.
• the poly-1-butene resin composition according to the invention is a composition comprising:
• the density of the polyethylene (B) is desired to be in the range of 0.94 to 0.98 g/cm 3 .
• the polyethylene (B) is homopolyethylene (B1) and the polypropylene (C) is homopolypropylene (C1).
• the polyethylene (B) and/or the polypropylene (C) may be used as a pigment dispersant. That is, in the poly-1-butene resin composition of the invention, a pigment (D) can be further contained.
• the poly-1-butene resin composition containing a pigment (D) according to the invention is preferably a composition comprising:
• the poly-1-butene resin composition of the invention is preferably a poly-1-butene resin composition capable of being molded into a pipe having an outer diameter of 15 mm and an inner diameter of 11 mm at a rate of 33 m/min.
• the poly-1-butene resin composition of the invention is favorably used for producing a pipe such as a cold or hot water pipe, particularly a cold or hot water supply color pipe.
• the pipe, the cold or hot water pipe and the cold or hot water supply color pipe according to the invention comprise the above-mentioned poly-1-butene resin composition of the invention.
• poly-1-butene resin composition according to the invention and the pipe comprising the composition are described in detail hereinafter.
• the poly-1-butene resin composition of the invention comprises a specific poly-1-butene resin (A), specific polyethylene (B) and/or specific polypropylene (B), and if necessary, a pigment (D).
• the poly-1-butene resin (A) for use in the invention is, for example, a homopolymer of 1-butene or a 1-butene/ ⁇ -olefin copolymer obtained by copolymerizing 1-butene with an ⁇ -olefin other than 1-butene, such as ethylene or propylene.
• the content of constituent units derived from an ⁇ -olefin other than 1-butene is not more than 40 % by mol, preferably not more than 20 % by mol, more preferably not more than 10 % by mol.
• Composition of the 1-butene/ ⁇ -olefin copolymer can be determined by measuring a 13 C-NMR spectrum of a sample solution obtained by homogeneously dissolving about 200 mg of the 1-butene/ ⁇ -olefin copolymer in 1 ml of hexachlorobutadiene in a sample tube with a diameter of usually 10 mm, under the measuring conditions of a measuring temperature of 120°C, a measuring frequency of 25.05 MHz, a spectral width of 1500 Hz, a pulse repetition time of 4.2 sec and a pulse width of 6 ⁇ sec.
• the melt flow rate (MFR, ASTM D 1238, 190°C, load of 2.16 kg) of the poly-1-butene resin (A) for use in the invention is in the range of 0.01 to 50 g/10 min, preferably 0.05 to 10 g/10 min, more preferably 0.1 to 0.8 g/10 min.
• the poly-1-butene resin (A) having a melt flow rate of the above range shows flexibility and has excellent creep resistance, impact resistance, abrasion resistance, chemical resistance and stress cracking resistance.
• the poly-1-butene resin (A) can be prepared by a hitherto known process, for example, a process of polymerizing 1-butene only or copolymerizing 1-butene with an ⁇ -olefin other than 1-butene, such as ethylene or propylene, in the presence of a Ziegler-Natta catalyst or a metallocene catalyst.
• the polyethylene (B) for use in the invention is homopolyethylene (B1) or an ethylene/ ⁇ -olefin copolymer (B2) obtained by copolymerizing ethylene with an ⁇ -olefin of 3 to 20 carbon atoms and containing constituent units derived from ethylene in amounts of not less than 50 % by mol and less than 100 % by mol.
• Examples of the ⁇ -olefins of 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene.
• propylene 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
• the polyethylene (B) for use in the invention has a viscosity-average molecular weight (Mv) of 900 to 29,000, preferably 2,000 to 20,000.
• Mv viscosity-average molecular weight
• a poly-1-butene resin composition having excellent high-speed moldability into colorless pipes can be obtained.
• the polyethylene (B) When a pigment (D) is used together with the polyethylene (B), preferably homopolyethylene (B1), the polyethylene (B) functions as a pigment dispersant, and hence a poly-1-butene resin composition having excellent high-speed moldability into color pipes can be obtained.
• the viscosity-average molecular weight (Mv) of the polyethylene (B) is measured in the following manner. A falling period of time (sec) is automatically measured at 135°C using an Atlantic type viscometer to determine a specific viscosity of a decalin solution of a sample. From the intrinsic viscosity ( ⁇ ) and the following formulas, the viscosity-average molecular weight (Mv) is calculated.
• ⁇ SP (t-t 0 )/t 0 wherein ⁇ SP is a specific viscosity, t 0 is a falling period of time (sec) of decalin, and t is a falling period of time (sec) of a sample solution.
• C sample weight/0.549358 wherein C is a solution concentration.
• ( ⁇ ) ⁇ SP/C(1+K ⁇ SP) wherein K is a constant and is 0.28.
• Mv 5.37 ⁇ 10 4 ⁇ ( ⁇ ) 1.37
• the density (JIS K 6760) of the polyethylene (B) such as homopolyethylene (B1) for use in the invention is desired to be in the range of 0.94 to 0.98 g/cm 3 , preferably 0.95 to 0.98 g/cm 3 .
• the crystallinity of the polyethylene (B), as measured by X-ray diffractometry, is desired to be in the range of 80 to 95 %.
• the low-molecular weight and high-density polyethylene (B) by polymerizing ethylene or copolymerizing ethylene with an ⁇ -olefin of 3 to 20 carbon atoms in the presence of a known olefin polymerization catalyst such as a Ziegler type olefin polymerization catalyst.
• the polyethylene (B) may be a thermal decomposition product of high-molecular weight polyethylene.
• the polyethylene (B) is used in an amount of 0.001 to 5 parts by weight, preferably 0.001 to 2 parts by weight, more preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the poly-1-butene resin (A).
• the polyethylene (B), particularly the homopolyethylene (B1) is used in the above amount, a poly-1-butene resin composition having excellent high-speed moldability into pipes can be obtained.
• the polypropylene (C) for use in the invention is homopolypropylene (C1) or a propylene/ ⁇ -olefin copolymer (C2) obtained by copolymerizing propylene with an ⁇ -olefin of 2 to 20 carbon atoms other than propylene and containing constituent units derived from propylene in amounts of not less than 50 % by mol and less than 100 % by mol.
• Examples of the ⁇ -olefins of 2 to 20 carbon atoms other than propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene.
• preferable are ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
• the polypropylene (C) for use in the invention has a viscosity-average molecular weight (Mv) of 900 to 29,000, preferably 3,000 to 29,000, more preferably 7,000 to 29,000.
• Mv viscosity-average molecular weight
• a poly-1-butene resin composition having excellent high-speed moldability into colorless pipes can be obtained.
• the polypropylene (C) When a pigment (D) is used together with the polypropylene (C), preferably homopolypropylene (C1), the polypropylene (C) functions as a pigment dispersant, and hence a poly-1-butene resin composition having excellent high-speed moldability into color pipes can be obtained.
• the viscosity-average molecular weight (Mv) of the polypropylene (C) is measured in the same manner as to measure the viscosity-average molecular weight (Mv) of the polyethylene (B).
• the constant K in the aforesaid formula is 0.38.
• the density (JIS K 6760) of the polypropylene (C) such as homopolypropylene (C1) for use in the invention is desired to be in the range of 0.89 to 0.93 g/cm 3 .
• the crystallinity of the polypropylene (C), as measured by X-ray diffractometry, is desired to be in the range of 50 to 70 %.
• the low-molecular weight polypropylene (C) such as homopolypropylene (C1) may be a product obtained by thermal decomposition of homopolypropylene having a viscosity-average molecular weight (Mv) of more than 29,000, or may be one obtained by directly polymerizing homopolypropylene having a viscosity-average molecular weight (Mv) of 900 to 29,000.
• the low-molecular weight propylene/ ⁇ -olefin copolymer (C2) by copolymerizing propylene with an ⁇ -olefin of 2 to 20 carbon atoms other than propylene in the presence of a known olefin polymerization catalyst such as a Ziegler type olefin polymerization catalyst.
• the polypropylene (C) is used in an amount of 0.001 to 5 parts by weight, preferably 0.001 to 2 parts by weight, more preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the poly-1-butene resin (A).
• the polypropylene (C), particularly the homopolypropylene (C1) is used in the above amount, a poly-1-butene resin composition having excellent high-speed moldability into pipes can be obtained.
• the pigment (D) that is optionally used in the invention is a hitherto known pigment and is a pigment usually used for cold or hot water pipes such as cold or hot water supply pipes.
• pigments examples include carbon black, rutile titanium, ultramarine, isoindolenone red, titanium yellow, quinacridone red, perylene red, condensed azo red, isoindolenone orange, isoindolenone yellow, phthalocyanine blue, phthalocyanine green and red iron oxide.
• These pigments can be used singly or in combination of two or more kinds.
• the pigment (D) is used in an amount of usually 0.05 to 10 parts by weight based on 100 parts by weight of the poly-1-butene resin (A), thought the amount varies depending upon the intended color of the pipe, the type of the pigment and the like.
• the poly-1-butene resin composition according to the invention comprises the poly-1-butene resin (A), the polyethylene (B) and/or the polypropylene (C), and if necessary, the pigment (D), as described above.
• the poly-1-butene resin composition of the invention is preferably a poly-1-butene resin composition capable of being molded into a colorless or color pipe having an outer diameter of 15 mm and an inner diameter of 11 mm at a rate of 33 m/min.
• the poly-1-butene resin composition of the invention can be prepared by, for example, melt kneading the components in the aforesaid specific ratio.
• the kneading can be carried out using a kneading device, such as a single-screw extruder, a twin-screw extruder, a twin-screw kneader or a Banbury mixer.
• a kneading device such as a single-screw extruder, a twin-screw extruder, a twin-screw kneader or a Banbury mixer.
• the poly-1-butene resin composition of the invention can be prepared also by melt kneading a masterbatch comprising the poly-1-butene resin (A), the polyethylene (B) and/or the polypropylene (C), and optionally, the pigment (D), with the poly-1-butene resin (A) . It is preferable to prepare the poly-1-butene resin composition of the invention using the masterbatch from the viewpoint of cost reduction due to rationalization.
• additives such as heat stabilizer, weathering stabilizer, antistatic agent, mildewproofing agent, rust preventive, lubricant and filler, may be optionally added in amounts not detrimental to the objects of the invention.
• the pipe, the cold or hot water pipe and the cold or hot water supply color pipe according to the invention comprise the poly-1-butene resin composition described above.
• These pipes usually have an inner diameter of 3 to 500 mm, an outer diameter of 5 to 600 mm and a wall thickness of 1 to 50 mm.
• the pipe, the cold or hot water pipe and the cold or hot water supply color pipe according to the invention can be produced by an extrusion molding method hitherto known.
• the poly-1-butene resin composition of the invention contains specific polyethylene and/or specific polypropylene and optionally a pigment in addition to a specific poly-1-butene resin, so that the composition has excellent high-speed moldability into colorless or color pipes.
• colorless or color pipes can be produced at a molding rate almost equal to or higher than the highest molding rate (25 m/min) to produce the conventional colorless pipes, and hence the composition is favorable for application to cold or hot water pipes, particularly cold or hot water supply color pipes.
• the pipe, the cold or hot water pipe and the cold or hot water supply color pipe according to the invention comprise the poly-1-butene resin composition having excellent high-speed moldability, and hence they are excellent in productivity and their production cost can be reduced.
• a masterbatch consisting of 69.3 parts by weight of a poly-1-butene resin (PB, density (ASTM D 1505): 0.918 g/cm 3 , melt flow rate (ASTM D 1238, 190°C, load of 2.16 kg): 0.5 g/10 min), 16.7 parts by weight of titanium white, 0.4 part by weight of carbon black, 3.6 parts by weight of ultramarine and 10.0 parts by weight of homopolyethylene (PE (1), viscosity-average molecular weight (Mv) : 4,000, density (JIS K 6760): 0.98 g/cm 3 , crystallinity: 85 %, melting point: 126°C) as a pigment dispersant were prepared.
• PE viscosity-average molecular weight
• JIS K 6760 density
• the pellets of the poly-1-butene resin composition were extrusion molded under the following conditions to obtain a gray pipe having an outer diameter of 15 mm, an inner diameter of 11 mm and a wall thickness of 2 mm.
• the molding rate to produce the pipe was 33 m/min, and the appearance of the pipe was good.
• Extruder extruder equipped with gear pump (article number: SX-90), manufactured by Ikegai K.K.
• the tensile test was carried out under the following conditions. Size of specimen: 2 mm (thickness) ⁇ 60 mm (length) ⁇ 5 mm (width)
• a gray pipe having an outer diameter of 15 mm, an inner diameter of 11 mm and a wall thickness of 2 mm was produced in the same manner as in Example 1.
• the molding rate to produce the pipe was 33 m/min, and the appearance of the pipe was good.
• a gray pipe having an outer diameter of 15 mm, an inner diameter of 11 mm and a wall thickness of 2 mm was produced in the same manner as in Example 1.
• the molding rate to produce the pipe was 33 m/min, and the appearance of the pipe was good.
• a gray pipe having an outer diameter of 15 mm, an inner diameter of 11 mm and a wall thickness of 2 mm was produced in the same manner as in Example 1.
• the molding rate to produce the pipe was 33 m/min, and the appearance of the pipe was good.
• a gray pipe having an outer diameter of 15 mm, an inner diameter of 11 mm and a wall thickness of 2 mm was produced in the same manner as in Example 1.
• the molding rate to produce the pipe was 18 m/min, and the appearance of the pipe was good.
• a gray pipe having an outer diameter of 15 mm, an inner diameter of 11 mm and a wall thickness of 2 mm was produced in the same manner as in Example 1.
• the molding rate to produce the pipe was 18 m/min, and the appearance of the pipe was good.
• a pipe having an outer diameter of 15 mm, an inner diameter of 11 mm and a wall thickness of 2 mm was produced in the same manner as in Example 1, except that only the poly-1-butene resin (PB) was used instead of the poly-1-butene resin composition.
• the molding rate to produce the pipe was 25 m/min, and the appearance of the pipe was good.
• Example 1 The procedure of Example 1 or Example 3 was repeated, except that the pigment dispersant was used in the amount shown in Table 1. The results are set forth in Table 1.

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Rigid Pipes And Flexible Pipes (AREA)
• Manufacture Of Macromolecular Shaped Articles (AREA)

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• 2001
  • 2001-01-15 JP JP2001006280A patent/JP4425479B2/ja not_active Expired - Lifetime
  • 2001-02-14 AU AU21216/01A patent/AU776237B2/en not_active Ceased
  • 2001-02-15 KR KR1020010007421A patent/KR100712628B1/ko active IP Right Grant
  • 2001-02-16 CN CNB01104568XA patent/CN1152917C/zh not_active Expired - Lifetime
  • 2001-02-19 EP EP01301424A patent/EP1125981B1/fr not_active Expired - Lifetime
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